CN112708160A - Polymer-based composite material for capacitor and preparation method thereof - Google Patents
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Abstract
The invention relates to a polymer matrix composite material for a capacitor and a preparation method thereof, wherein the polymer matrix composite material for the capacitor is characterized in that: the polymer-based composite material comprises an upper layer of composite material and a lower layer of composite material, wherein the composite material positioned on the upper layer is a polymer PEI/two-dimensional material composite material, and the composite material positioned on the lower layer is a polymer PEI/oxide array composite material. The polymer matrix composite material can stably work at room temperature to 150 ℃, and has high energy storage performance.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a polymer matrix composite material for a capacitor and a preparation method thereof.
Background
The high-energy-density high-voltage pulse dielectric material and the capacitor have the advantages of high power density, high charging and discharging speed, cyclic aging resistance, stable performance and the like, are important power type energy storage devices, and play a key role in high-power energy storage and pulse power systems such as power grid frequency modulation, key medical equipment, industrial lasers, new energy vehicles, advanced electromagnetic weapons and the like.
Higher demands are currently placed on the new generation of dielectric capacitors, which need to be able to operate stably in environments far above room temperature. For example, in the fields of aviation and aerospace, the centralized architecture of a traditional engine monitoring system is converted into a distributed control scheme, so that the interconnection complexity can be reduced, the airplane weight can be saved by hundreds of pounds, and a plurality of electronic component devices must be placed near an engine with the temperature of 200 ℃ and 300 ℃; with the progress of silicon-on-insulator technology and the development of wide-band-gap semiconductor materials, the working temperature of semiconductors has been expanded to 200 ℃ or even higher; electronic capacitors used with these circuits also need to withstand the same harsh conditions in high temperature electrical appliances. In addition, some hybrid electric vehicle electronic control systems use a cooling system to reduce the ambient temperature from 120-140 ℃ to 70-80 ℃. However, the presence of a cooling system will undoubtedly increase the mass and volume of the power system, reducing fuel efficiency. Therefore, the research on the pulse capacitor which can stably work in a high-temperature (not less than 150 ℃) environment and has high energy storage density is a problem which needs to be solved urgently in the high-tech field.
A polymer-based (inorganic-organic) composite is a typical capacitor energy storage material. The early stage literature shows that the microstructure (the shape, the size, the orientation and the volume fraction of the inorganic filler) of the composite energy storage material can effectively regulate and control the polarization characteristic and the energy storage capacity of the composite material. The introduction of the one-dimensional high-orientation filler in the composite material is beneficial to greatly improving the polarizability of the composite energy storage material under the condition of lower volume fraction and increasing the energy storage density and power density; and the two-dimensional filler is introduced into the polymer matrix, so that efficient conduction barriers can be established, charge movement is limited, the growth of an electronic tree in the breakdown process is hindered, the breakdown-resistant field intensity is improved, and the energy storage density and the power density are increased.
At present, most researches on high-energy-storage high-power polymer-based composite materials focus on the energy storage performance at room temperature, for example, the invention patent of China, ZL201310075684.7 (publication No. CN104044318B), discloses that the laminated structure of the polymer-based dielectric energy storage composite material can obtain good high energy storage density and high breakdown field strength, but a film capacitor taking the polymer dielectric material as a main body has poor thermal stability and is difficult to stably work in a high-temperature environment. Particularly, under the action of a high electric field, the increase of the temperature can lead the internal leakage current of the polymer dielectric to be in an exponential rising trend, so that the charge-discharge efficiency and the energy storage density are sharply reduced, and the application requirement is difficult to meet.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a polymer-based composite material for a capacitor, which is stable in operation at high temperature and has high energy storage density, in view of the above-mentioned current state of the art.
The second technical problem to be solved by the invention is to provide a preparation method of a polymer-based composite material capable of realizing mass production.
The technical scheme adopted by the invention for solving the first technical problem is as follows: a polymer matrix composite for a capacitor, characterized by: the polymer-based composite material comprises an upper layer of composite material and a lower layer of composite material, wherein the composite material positioned on the upper layer is a polymer PEI/two-dimensional material composite material, and the composite material positioned on the lower layer is a polymer PEI/oxide array composite material.
Preferably, the thickness of upper composite is 2 ~ 30um, and the thickness that is located lower floor's composite is 2 ~ 10 um.
Preferably, the two-dimensional material is one of a hexagonal boron nitride nanosheet, an alumina nanosheet, a montmorillonite nanosheet and a titanium dioxide nanosheet, and the oxide array is one of zinc oxide, barium titanate, titanium dioxide and strontium titanate.
The technical scheme adopted by the invention for solving the second technical problem is as follows: a method for preparing a polymer matrix composite, comprising the steps of:
1) preparing an oxide nano-array inorganic filler:
adding tetrabutyl titanate into a mixed solution of oxides containing hydrochloric acid and deionized water, wherein the tetrabutyl titanate, the hydrochloric acid and the deionized water are mixed according to a volume ratio of 1 (25-35): (25-35), stirring to form a uniform transparent solution; the clear solution was then transferred to an FTO substrate in an autoclave at temperature T1The reaction time t is 170-200 DEG C1Cooling to room temperature for 0.5-3 h, taking the FTO substrate out of the high-pressure kettle, and washing with deionized water and ethanol respectively;
2) preparing a two-dimensional nano material inorganic filler:
stirring the nano powder for 20-25 h under the amplitude of 250-350 mA; subsequently, placed in a centrifuge tube and rotated at a rotational speed n1Centrifuging at 2000-4000 rpm for 20-40 min, and collecting supernatant to separate un-peeled powder; then, the supernatant is subjected to rotation at n2Centrifuging at 9000-11000 rpm for 20-40 min, and collecting sediments on the wall of the centrifugal tube, wherein the sediments are two-dimensional nano inorganic filler;
3) preparation of Polymer-based composite Material
First PEI is dissolved in NMP at a temperature T5Stirring at 40-60 ℃ to prepare a PEI solution; subsequently dispersing the sediment in the step 2) in NMP, and ultrasonically stirring for a time t5The reaction solution is slowly added into the mixture under stirring for 15-30 min to form a stable PEI/two-dimensional material suspension, and the polymer substrate is formed after bubbles are removed in a vacuum oven for 15-25 min; spin coating PEI solution on the oxide nano array inorganic filler obtained in the step 1) by adopting a spin coating method to form a one-dimensional oxide nano array composite material; finally, the PEI/two-dimensional material suspension is coated on the composite material for forming the one-dimensional oxide nano arrayThereby forming the final laminated composite.
Preferably, in step 1), the volume of tetrabutyl titanate is 1ml, the volumes of hydrochloric acid and deionized water are both 30ml, and the temperature T1 is 180 ℃.
Preferably, in step 2), the stirring time t0Is 24h, the rotating speed n1Is 3000rpm and at this speed the centrifugation time t3Is 30 min; speed n210000rpm, and a centrifugation time t at the rotation speed4It is 30 min.
In order to allow the oxide nano-array inorganic filler to be better crystallized, it is preferable that the oxide nano-array inorganic filler prepared in the step 1) is heat-treated at a heat treatment temperature T2At 450-750 ℃ for a heat treatment time t2Is 1.5 to 2.5 hours. If the heat treatment temperature is too high and the heat preservation time is too long, the defects in the aspect of the capacitor performance are easily caused, so that the improvement of the energy storage density and the thermal stability performance is influenced; if the heat treatment temperature is too low and the heat preservation time is too short, the organic salt is not completely decomposed to form a target product; the adoption of the heat treatment conditions is beneficial to the improvement of the capacitive performance.
In order to dry the prepared two-dimensional nano-material inorganic filler, the two-dimensional nano-material inorganic filler prepared in the step 2) is preferably dried at a drying temperature T4The temperature is 60-80 ℃, and the drying time is 10-14 h.
Preferably, in step 3), the mass of PEI is 1g and the amount of NMP is 5ml, and after stirring at a temperature of 50 ℃ a PEI solution is prepared, and the ultrasonic stirring is carried out for a time t5For 20min, the polymer substrate was formed 20min after bubble removal. In this way, it is advantageous to make the deposit more uniformly dispersed.
Preferably, the polymer matrix composite prepared in step 3) is subjected to a heat treatment at a temperature T7At 140-220 ℃, and the heat preservation time t7Is 20min to 40 min. After the heat treatment is adopted for treatment, the defects in the composite material can be eliminated.
Compared with the prior art, the invention has the advantages that: the upper layer is made of the polymer PEI/two-dimensional material composite material, the lower layer is made of the polymer PEI/oxide array composite material, the lower layer is favorable for improving the dielectric constant, the upper layer is favorable for improving the breakdown field intensity, and the upper layer of the polymer PEI/two-dimensional material composite material is matched with the lower layer of the polymer PEI/oxide array composite material, so that the laminated polymer matrix composite material can stably work at room temperature to 150 ℃. The preparation method has low cost, and the thickness of the upper layer and the lower layer is controllable, so that the mass production can be realized, and the requirements are met.
Drawings
FIG. 1 is a schematic structural view of a polymer matrix composite of example 1;
FIG. 2 is a graph of the energy storage density and efficiency of the polymer matrix composite of example 1 at 150 ℃;
FIG. 3 is a graph of the cycling stability at 150 ℃ of the polymer matrix composite of example 1.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1:
as shown in fig. 1 to 3, the present invention is the 1 st preferred embodiment.
As shown in fig. 1, the capacitor includes an upper plate 1, a lower plate 2, and a polymer matrix composite between the upper plate 1 and the lower plate 2. The polymer-based composite material has an upper layer and a lower layer, wherein the composite material on the upper layer is a polymer PEI/two-dimensional material composite material 3, the composite material on the lower layer is a polymer PEI/oxide array composite material 4, the thickness of the upper layer composite material is 2-30 um, and the thickness of the lower layer composite material is 2-10 um.
The preparation method of the polymer matrix composite material comprises the following steps:
1) preparing oxide nano-array inorganic filler, wherein the oxide array adopts TiO2Nano-array:
adding tetrabutyl titanate into TiO containing hydrochloric acid and deionized water2Wherein, tetrabutyl titanate, hydrochloric acid and deionized water are mixed according to the volume ratio of 1: 30: 30, wherein the tetrabutyl titanate is 1ml, and stirring is carried out to form a uniform transparent solutionLiquid; then transferring the transparent solution to an FTO substrate in an autoclave, reacting at the temperature T1 of 180 ℃ for 3h at the time T1, taking the FTO substrate out of the autoclave after cooling to the room temperature, and washing with deionized water and ethanol respectively to obtain TiO2Nano-array inorganic filler; for better crystallization, the TiO to be prepared2Nano array inorganic filler at heat treatment temperature T2Heat treatment is carried out at 500 ℃ for a time t2Is 2 h;
the volume of the high-pressure autoclave is 100ml, and an FTO substrate is 4cm multiplied by 2 cm; in this example, the FTO is fluorine-doped tin oxide, the PEI is polyetherimide, and the glass transition temperature of the PEI is 200-.
2) Preparing a two-dimensional nano-material inorganic filler, wherein the two-dimensional nano-material adopts boron nitride nano-sheets (BNNS):
stirring 70-BN type powder under the amplitude of 300mA for a time t0Is 24 hours; subsequently, placed in a centrifuge tube and rotated at a rotational speed n1At a centrifugation time t of 3000rpm3For 30min, collecting supernatant to separate un-peeled powder; then, the supernatant is subjected to rotation at n2Is the centrifugation time t at 10000rpm4For 30min, collecting the deposit on the wall of the centrifuge tube, then placing the deposit BNNs in a vacuum oven at a drying temperature T4Drying at 70 ℃ for 12h, wherein the deposit in the step is a two-dimensional nano-material inorganic filler, namely a BNNs inorganic filler;
3) preparation of polymer-based composite:
1g PEI was first dissolved in 5ml NMP at a temperature T5Preparing a PEI solution after stirring at 50 ℃; subsequently, the BNNs inorganic filler in the step 2) is dispersed in NMP, and the ultrasonic stirring time is t5The reaction solution is stirred for 20min, and then slowly added into the mixture to form a stable BNNs/PEI suspension, and a polymer substrate is formed after bubbles are removed in a vacuum oven for 20 min; spin coating PEI solution on the TiO of step 1) by spin coating method2Nano array inorganic filler to form one-dimensional TiO2A column nano-array composite; finally, the BNNs/PEI suspension is coated to form one-dimensional TiO2Nano array complexCompounding the materials to form the final laminated polymer matrix composite (TiO)2-PEI/BN-PEI); then, the prepared polymer matrix composite material is dried for 2 hours in vacuum at 70 ℃ so as to completely evaporate the solvent; finally, the prepared polymer matrix composite material is subjected to heat treatment, wherein the temperature T of the heat treatment7At 150 ℃ for a heat treatment time t7It is 30 min.
The above-mentioned removal of bubbles t6The time is 20min, and NMP is N-methylpyrrolidone.
As shown in FIG. 2, in order to show the variation curve of increasing energy storage density and decreasing efficiency with increasing electric field, it can be seen from FIG. 2 that the polymer-based composite material prepared by the above preparation method has excellent energy storage performance and higher efficiency at 150 ℃, wherein the energy storage density under the electric field of 400MV/m is 10.36J/cm3The efficiency was 82.6%.
As shown in FIG. 3, the polymer-based composite material prepared by the preparation method has good cycling stability at 150 ℃, wherein the polymer-based composite material can still work normally after being cycled at 150 ℃ for 50000 times.
Example 2:
this embodiment differs from embodiment 1 described above only in that: in step 1), the transparent solution is transferred to an FTO substrate in an autoclave at a temperature T1At 180 ℃ for a reaction time t1Is 2 h; in step 2) the amplitude was 250mA, in step 3) the polymer matrix composite was at a temperature T7At 200 ℃ for a heat treatment time t7It is 30 min. The polymer-based composite material prepared by the embodiment can still normally work after 50000 times of circulation at 150 ℃, so that the polymer-based composite material prepared by the embodiment has good circulation stability and higher energy storage density at room temperature to 150 ℃, and the energy storage density is 10.3J/cm3。
Example 3:
this embodiment differs from embodiment 1 described above only in that: in step 1), the transparent solution is transferred to an FTO substrate in an autoclave at a temperature T1At 180 ℃ for a reaction time t1Is 1h; in step 2), the amplitude was 350 mA.
Example 4:
this embodiment differs from embodiment 1 described above only in that: in step 1), the transparent solution is transferred to an FTO substrate in an autoclave at a temperature T1At 180 ℃ for a reaction time t1It is 30 min.
Example 5:
this embodiment differs from embodiment 1 described above only in that: the thickness of the composite material layer positioned on the upper layer is 2um, and the thickness of the composite material layer positioned on the lower layer is 2 um; the oxide array is a barium titanate array, the two-dimensional material is an aluminum oxide nanosheet, and the parameters in the preparation method are selected differently, specifically as shown in the following table 1.
Example 6:
this embodiment differs from embodiment 1 described above only in that: the thickness of the composite material layer positioned on the upper layer is 15um, and the thickness of the composite material layer positioned on the lower layer is 10 um; the oxide array is a zinc oxide array, the two-dimensional material is a montmorillonite nanosheet, and the parameters in the preparation method are selected differently, which is specifically shown in the following table 1.
Example 7:
this embodiment differs from embodiment 1 described above only in that: the thickness of the composite material layer positioned on the upper layer is 30um, and the thickness of the composite material layer positioned on the lower layer is 8 um; the oxide array is made of strontium titanate, the two-dimensional material is made of titanium dioxide nanosheets, and the parameters in the preparation method are selected differently, which is shown in the following table 1.
Table 1: selection of specific parameters in the preparation method of the above 7 examples
Claims (10)
1. A polymer matrix composite for a capacitor, characterized by: the polymer-based composite material comprises an upper layer of composite material and a lower layer of composite material, wherein the composite material positioned on the upper layer is a polymer PEI/two-dimensional material composite material, and the composite material positioned on the lower layer is a polymer PEI/oxide array composite material.
2. The polymer-matrix composite according to claim 1, wherein: the thickness of upper composite is 2 ~ 30um, and the thickness that is located lower floor's composite is 2 ~ 10 um.
3. The polymer-matrix composite according to claim 1, wherein: the two-dimensional material is one of hexagonal boron nitride nanosheets, alumina nanosheets, montmorillonite nanosheets and titanium dioxide nanosheets, and the oxide array is one of zinc oxide, barium titanate, titanium dioxide and strontium titanate.
4. A method of preparing a polymer matrix composite according to any one of claims 1 to 3, comprising the steps of:
1) preparing an oxide nano-array inorganic filler:
adding tetrabutyl titanate into a mixed solution of oxides containing hydrochloric acid and deionized water, wherein the tetrabutyl titanate, the hydrochloric acid and the deionized water are mixed according to a volume ratio of 1 (25-35): (25-35), stirring to form a uniform transparent solution; then transferring the transparent solution to an FTO substrate in an autoclave, and reacting at the temperature T1 of 170-200 ℃ for a time T1Cooling to room temperature for 0.5-3 h, taking the FTO substrate out of the high-pressure kettle, and washing with deionized water and ethanol respectively;
2) preparing a two-dimensional nano material inorganic filler:
stirring the nano powder for 20-25 h under the amplitude of 250-350 mA; then, placing the powder in a centrifugal tube, centrifuging the powder at the rotating speed n1 of 2000-4000 rpm for 20-40 min, and collecting supernatant to separate the powder which is not peeled off; centrifuging the supernatant for 20-40 min at a rotating speed n2 of 9000-11000 rpm, and collecting sediments on the wall of the centrifugal tube, wherein the sediments are two-dimensional nano-material inorganic fillers;
3) preparation of Polymer-based composite Material
First PEI is dissolved in NMP at a temperature T5Stirring at 40-60 ℃ to prepare a PEI solution; subsequently dispersing the sediment in the step 2) in NMP, and ultrasonically stirring for a time t5The reaction solution is slowly added into the mixture under stirring for 15-30 min to form a stable PEI/two-dimensional material suspension, and the polymer substrate is formed after bubbles are removed in a vacuum oven for 15-25 min; spin coating PEI solution on the oxide nano array inorganic filler obtained in the step 1) by adopting a spin coating method to form a one-dimensional oxide nano array composite material; finally, the PEI/two-dimensional material suspension is coated to form a one-dimensional oxide nano array composite material, thereby forming a final laminated composite material.
5. The method of claim 4, wherein: in the step 1), the volume of tetrabutyl titanate is 1ml, the volumes of hydrochloric acid and deionized water are both 30ml, and the temperature T is1It was 180 ℃.
6. The method of claim 4, wherein: in step 2), stirring for a time t0Is 24h, the rotating speed n1Is 3000rpm and at this speed the centrifugation time t3Is 30 min; speed n210000rpm, and a centrifugation time t at the rotation speed4It is 30 min.
7. The method of claim 4, wherein: carrying out heat treatment on the oxide nano-array inorganic filler prepared in the step 1), wherein the heat treatment temperature is T2At 450-550 ℃, for a heat treatment time t2Is 1.5 to 2.5 hours.
8. The method of claim 4, wherein: drying the two-dimensional nano material inorganic filler prepared in the step 2) at a drying temperature T4The temperature is 60-80 ℃, and the drying time is 10-14 h.
9. The method of claim 4, wherein: in step 3), the mass of PEI is1g, NMP 5ml, and at temperature T5Preparing PEI solution after stirring at 50 ℃, and stirring for time t by ultrasonic5For 20min, the polymer substrate was formed 20min after bubble removal.
10. The method of claim 4, wherein: carrying out heat treatment on the polymer matrix composite material prepared in the step 3), wherein the heat treatment temperature T is7At 140-220 ℃, and the heat preservation time t7Is 20min to 40 min.
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